In this report we present micro/nanostructuring of novel metal isopropoxides-silica containing hybrid sol-gel materials by the femtosecond laser direct writing technique and apply it for the fabrication of various microoptical/nanophotonic components. This approach enables one to photostructure true three-dimensional objects with controlled sub-100 nm spatial definition. Due to self-smoothing effects, surface roughness can be formed below 30 nm making this technique widely applicable for microoptical/nanophotonics devices in visible and near-infra-red wavelengths. After photopolymerization, these materials inherit desired optical properties: high transmittance in the 400–1500 nm spectral range and nearly glass-matching optical refractive index. Doping with organic dyes or quantum dots offers additional functionalities. Fields of applications cover: light guiding, coupling/extraction, trapping, signal processing and transferring, microscopy, biology, etc. In brief, we investigated direct laser writing structurability of these materials and its optimization for manufacturing microoptical/nanophotonic components. We successfully produced microoptical components such as aspheric and Fresnel lenses. We demonstrate the flexibility and reproducibility of this approach to fabricate custom-shaped elements on the tip of the optical fiber, thus producing integrated microoptical devices. The micro/nanostructures were characterized by optical and scanning electron microscopies, and optical profilometry. Their optical functions were measured using a custom-built setup to serve the purpose. The obtained values were in close coincidence to the theoretical values. Further research in the direction of production integrated and multifunctional components to be applied in the fields of photonics, plasmonics and telecommunications as well as optofluidics is currently being carried out.